The present invention relates to 2,2,6-trimethyl-1-cyclohexene-1-ylacetaldehyde (or "beta-cyclohomocitral") produced by, interalia, a novel process described and claimed in copending Applications for U.S. Ser. No. 507,414, filed on Sept. 19, 1974 now U.S. Pat. No. 3,956,393 issued on May 4, 1976 and Ser. No. 594,100 filed on July 8, 1975, and novel compositions using such beta-cyclohomocitral to alter, modify, enhance the aroma of a perfumed composition or a perfumed article or enhance the aroma of a perfumed composition or perfumed article.
There has been considerable work performed relating to substances which can be used to impart, modify, alter or enhance fragrances to (or in) various consumable materials such as perfumed compositions and perfumed articles such as soaps, colognes and detergents. These substances are used to diminish the use of natural materials, some of which may be in short supply and/or to provide more uniform properties in the finished product. Woody, camphoraceous, green, rosey, floral and earthy notes are desirable in several types of perfumed compositions and perfumed articles.
Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", isocyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta cyclotrylidene acetaldehyde", thus:
(i) 760 CYCLOCITRAL PA0 (ii) "761: iso-CYCLOCITRAL PA0 (iii) "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE ##STR8## Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones. PA0 (iv) "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE PA0 (v) "869: DEHYDRO-beta-CYCLOCITRAL (Safranal)
Alpha-cyclocitral= (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde). beta-cyclocitral= (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##STR5## Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different odors." PA2 A mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral). ##STR6## 2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cyclocitral). ##STR7## Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet-green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil. PA2 Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates from sweetness and lifts the topnote), with Inonoes (freshness), Geranium "vegetable" notes), etc. . . . " PA2 Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. . . ." PA2 2,6,6-trimethyl-1-cyclohexenyl-beta-acrolein. ##STR9## Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone. PA2 Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. . . ." PA2 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##STR10## Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron). PA2 Interesting material for fresh topnotes, as a modifier for aldehydric-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils. . . ."
Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole and Berthet, Helv. Chim. Acta. 55 Fasc-6, 1866 (1972).